Certain oxyalkylated derivatives of fusible resins



Feb. 24, 1953 M. DE GROOTE ETAL 2,529,704

CERTAINYOXYALKYLATED DERIVATIVES OF FUSIBLE RESINS Original Filed Nov.28, 1949 IOO% VYVY M/M\ PHENOL-ALDEHYDE D RESIN |oo/., 0%

, INVE RS Me n DeGro Ber h rd Keiser ATTORNEYS Patented Feb. 24, 1953CERTAIN OXYALKYLATED DERIVATIVES OF FUS'IBLE RESIN S Melvin De Groote,St. Louis and Bernhard Keiser,

Webster Groves, Mo., assignors to Petrolite Corporation, Wilmington,Del., a corporation of Delaware Continuation of application Serial No.129,708, November 28, 1949. This application May 24, 1952, Serial No.289,771

6 Claims. 1

The present invention is concerned with certain new chemical products,compounds, or compositions which have useful application in variousarts. This application is a continuation of our application Serial No.129,708, filed November 28, 1949, and now abandoned.

Our Patent 2,557,081, granted June 19, 1951, on an application filedconcurrently with said application Serial No. 129,708, describes thebreaking of petroleum emulsions by means of certain resins oxyalkylatedwith both ethylene oxide and propylene oxide in stated relativeproportions. The new products of the present application are a smallgroup of the compositions described in our said patent, whichcompositions have outstanding properties, presumably because of thespecific proportions of the three constitu ents, the resin, the ethyleneoxide, and the propylene oxide, from which they are prepared.

Our Patent 2,499,370, granted March 7, 1950,

describes certain hydrophile synthetic products which are theoxyalkylation products of alpha, beta-alkylene oxides having not morethan four carbon atoms and oxyalkylation-susceptible, fusible, organicsolvent-soluble, Water-insoluble phenolaldehyde resins, which resins arederived from difunctional monohydric phenols and aldehydes having notover eight carbon atoms. The resins described as reactants for theproduction of the demulsifiers of our said patent are those used inproducing the particular small class of 'oxyalkylated products of thepresent applica tion, except that, whereas resins described in saidpatent are derived from difunctional phenols in which R is a hydrocarbonradical having 4 to 14 carbon atoms and substituted inthe ortho or paraposition is oxyalkylated with both ethylene oxide and propylene oxide,in such weight proportions of the three reactants as to come within thearea defined by points I, 2, 3, 4, 5, and 6, and advantageously the areadefined by points I, I, 8, and 9 on the accompanying chart, which is aconventional representation of a 3-component system, proportions beingweight proportions of the three components. The line l-5 representsabout 4% resin; the line l--'| about 50% ethylene oxide; the line 1-8about 14% resin; and the line 8-9 about 66% ethylene oxide; while thelines connecting the other points are all on the 10% increment lines.

Products, as above described briefly, and hereinafter described indetail, are particularly effective in breaking petroleum emulsions ofthe water-in-oil type. Oi] field emulsions of this type are commonly.referred to as cut oil, roily oil, -emulsified oil, etc., and whichcomprise fine droplets of naturally-occurring waters or brines dispersedin a more or less permanent state throughout the oil which constitutesthe continuous phase of the emulsion.

' The new products herein described are useful as wetting, detergent andleveling agents in the laundry, textile and dyeing industries; aswetting agents and detergents in the acid washing of building stone andbrick; as wetting agents and spreaders in the application of asphalt inroad building and the like; as a flotation reagent in the flotationseparation of various aqueous suspensions containing negatively chargedparticles, such as sewage, coal washing waste water, and various tradewastes and the like; as germicides, insecticides, emulsifying agents,as, for example,

.for cosmetics, spray oils, water-repellent textile finishes, aslubricants, etc.

In our Patent 2,499,370, the application for which was copending withour said application Serial No. 129,708 We have described certain newproducts or compositions of matter which are of unusual value in certainindustrial applications requiring the use of products or compoundsshowing surface-activity. We have found that if solvent-soluble resinsare prepared from diiunctional (direactive) phenols in which one of thereactive (0 or 10) positions of the phenol is sub stituted by ahydrocarbon radical having 4 to 12 carbon atoms, in the substantialabsence of trifunctional phenols, and aldehydes having not over 8 carbonatoms, subsequent oxyalkylation, and specifically oxyethylation, yieldsproductsof unusual value for demulsification purposes,'provided thatoxyalkylation is continued to the degree that hydrophile properties areimpartedto the compound. By substantial absence of trivary with thenature of the other components of. the system; but in general theproportion of trithe resins in that patent for a discussion of theconsiderations involved in the production of suitable resins and toExamples 1a through 103a of that patent for specific examples of suchresins.

However, we wish to point out that in addition to the resins describedin our said patent, useful products of the present invention may beprepared from phenols having substituents having functional phenolswhich is tolerable in the con-' ventional resinification proceduresillustrated herein is quite small. In experiments following conventionalprocedure using an acid catalyst in which we have included trifunctionalphenols in "up ,to' 14 carbon atoms, as, for example, difunctional.tetradecyl phenols which are available at an attractive price- One gradeof these particular phenols consists of a mixture representing 'about90% para-substituted phenol, 5% orthoamounts of from 3% to about 1% orsomewhat less, based on the difunctional phenols, we have encountereddifficulties in preparing oxyalkylated substituted phenol,

and 5% meta-substituted phenol. Although the amount ofmeta-substituentis comparatively large compared with other derivativesof the type useful in the practice of this invention.

Such products are rarely a single chemical compound but are almostinvariably a mixture of cogeners. One useful type of compound may beexemplified in an idealized simplification in the following formula:

OH OH OH H r H R R R In these formulas n represents a numeral varyingfrom 1 to 13, or even more, provided that the parent resin is fusibleand organic solventsoluble; n represents a numeral varying from 1 to 20,with the proviso that the average value of n be at least 2; and R is ahydrocarbon radical having at least 4 and not over 12 carbon atoms.These numerical values of n and n"are, of course, on a statisticalbasis.

Said previously described invention or inventions involves the use, as ademulsifier, of a hydrophile oxyalkylated 2, 4, 6 (i. e., 2, 4, or 6) C4to C12 hydrocarbon-substituted monocyclic-phenol- C1- to Caz-aldehyderesin, in which the ratio of oxyalkylene groups to phenolic nuclei is atleast 2:1 and the alkylene radicals of the oxyalkylene groups areethylene, propylene, butylene, hy-

droxypropylene or hydroxybutylene correspond-,

ing to the alpha-beta alkylene oxides, ethylene oxide, alpha-betapropylene oxide, alpha-beta butylene oxide, glycide and methyl glycide.

We have found that if one uses both propylene oxide and ethylene oxideas the oxyalkylating agent in certain predetermined ratios, ashereinafter described, in a large number of instances one obtains a muchbetter demulsifier than is possible by the use of either alkylene oxidealone in the absence of the other alkylene oxides.

Stated another way, the same resins described in the aforementionedco-pending applications are employed as a raw material and subjected tooxyethylation with both ethylene oxide and pro,- pylene oxide. theresins used as raw materials for producing the products of thisinvention by reference to our said Patent 2,499,370, and specifically,we refer to the general discussion of the production of For this reasonwe will describe derived from a single phenol.

difunctional phenols, it appears unobjectionable, due to thecomparatively large side chain. For example, compare with thepreparation of soluble thermoplastic phenols from cardanol, or sidechain hydrogenated cardanol. One grade of this material is manufacturedby the O-ronite Chemical Co. and designated as tetradecyl phenol, grade14-60691. We have prepared resins from such phenol alone, or inadmixture, following the same procedure described in specific examplespreceding. As a specific example we have subsimilar characteristics,except that, if anything, the resins were somewhat darker and somewhatmore fluid. Similarly, tetradecyl phenol can be used in combination withthe other aldehydes described, and will, for practical purposes, actvery similarly to dodecyl phenol.

Obviously mixtures of reactants may be employed, as, for example, amixture of para-butylphenol and para-amylphenol, or a mixture ofpara-butylphenol and para-hexylphenol, or parabutylphenol andpara-phenylphenol. It is extremely diificult to depict the structure ofa resin When mixtures of phenols are used, even in equimolarproportions, the structure of the resin is even more indeterminable. Inother words, a mixture involving para-butylphenal and para-amylphenolmight have an alternation of the two nuclei, or one might have a seriesof butylated nuclei and then a series of amylated nuclei. If a mixtureof aldehydes is employed, for instance, acetaldehyde and butyraldehyde,or acetaldehyde and formaldehyde, or benzaldehyde and acetaldehyde, thefinal structure of the resin becomes even more complicated, and possiblydepends upon the relative reactivity of the aldehydes. For that matter,one might be producing simultaneously two different resins, in whatwould actually be a mechanical mixture, although such mixture mightexhibit someunique properties, as compared with a mixture of the sametwo resins prepared separately.

The oxyalkylation of resins of the kind from which the products used inthe practice of the present invention are prepared is advantageouslycatalyzed by the presence of an alkali. Useful alkaline catalystsinclude soaps, sodium acetate, sodium hydroxide, sodium methylate,caustic potash, etc. The amount of alkaline catalyst usually is between0.2% to 2%. I'he temperature employed may vary from room temperature toas high as 200 C. The reaction may be conducted with or withoutpressure, i. e., from zero pressure to approximately 200 or even 300pounds gauge pressure (pounds per square inch). In a general Way, themethod employed is substan- '5 tially the same procedure as'used foroxyalkylation of other organic materials having reactive phenolicgroups.

It may be necessary to allow for the acidity of a resin in determiningthe amount of alkaline catalyst to be added in oxyalkylation. Forinstance, if a nonvolatile strong acid such as sulfuric acid is used tocatalyze the resinification reaction, presumably after being convertedinto a sulfonic acid, it may be necessary and is usually advantageous toadd an amount of alkali equal stoichiometrically to such acidity, andinclude added alkali over and above this amount as the alkalinecatalyst.

It is advantageous to conduct the oxyethylation or oxypropylation in thepresence of an inert solvent such as xylene, cymene, decalin, ethyleneglycol diethylether, diethyleneglycol diethylether, or the like,although with many resins, the oxyalkylation proceeds satisfactorilywithout a solvent. Since xylene is cheap and may be permitted to bepresent in the final product used as a demulsifier, it is our preferenceto use xylene. This is particularly true in the manufacture of productsfrom low-stage resins, i. e., of 3 and up to and including 7 units permolecule.

If a xylene solution is used in an autoclave as hereinafter indicated,the pressure readings of course represent total pressure, that is, thecombined pressure due to Xylene and also due to ethylene or propyleneoxide. Under such circumstances it may be necessary at times to usesubstantial pressures to obtain effective results, for instance,pressures up to 300 pounds along with correspondingly high temperatures,if required.

However, even in the instance of high-melting resins, a solvent such asxylene can be eliminated in either one of two ways: After theintroduction of approximately 2 or 3 moles of ethylene oxide, forexample, per phenolic nucleus, there is a definite drop in the hardnessand melting point of the resin. At this stage, if xylene or a similarsolvent has been added, it can be eliminated by distillation (vacuumdistillation if desired) and the subsequent intermediate, beingcomparatively soft and solvent-free, can be reacted further in the usualmanner with ethylene oxide or some other suitable reactant.

Another procedure is to continue the reaction to completion with suchsolvent present and then eliminate the solvent by distillation in thecustomary manner.

Attention is directed to the fact that the resins herein described mustbe fusible or soluble in an organic solvent. Fusible resins invariablyare soluble in one or more organic solvents, such as those mentionedelsewhere herein. It is to be emphasized, however, that the organicsolvent employed to indicate or assure that the resin meets thisrequirement need not be the one used in oxyalkylation. Indeed solventswhich are susceptible to oxyalkylation are included in this group oforganic solvents. Examples of such solvents are alcohols andalcohol-ethers. However, where a resin is soluble in an organic solvent,there are usually available other organic solvents which are notsusceptible to oxyalkylation, useful for the oxyalkylation step. In anyevent, the organic solvent-soluble resin can be finely powdered, forinstance, to 100 to 200 mesh, and a slurry or suspension prepared inxylene or the like, and subjected to oxyalkylation. The fact that theresin is soluble in an organic solvent, or the fact that it is fusible,means that it consists of separate molecules. Phenol-aldehyde resins ofthe type herein specified possess reactive hydroxyl groups and areoxyalkylation susceptible.

Based on molecular weight determinations, most of the resins used,particularly in the absence of a secondary heating step, contain 3 to 6or 7 phenolic nuclei with approximately 4 /2 or 5 /2 nuclei as anaverage. More drastic conditions of resinification yield resins ofgreater chain length. Such more intensive resinification is aconventional procedure and may be employed if desired. Molecular weight,of course, is measured by any suitable procedure, particularly bycryoscopic methods; but using the same reactants and using more drasticconditions of resinification one usually finds that higher molecularweights are indicated by higher melting points of the resins and atendency to decreased solubility.

Either an alkaline or acid catalyst is advantageously used in preparingthe resin. A combination of catalysts is sometimes used in two stages:for instance, an alkaline catalyst is sometimes employed in a firststage, followed by neutralization and addition of a small amount of acidcatalyst in a second stage. It is generally believed that even in thepresence of an alkaline catalyst, the number of moles of aldehyde, suchas formaldehyde, must be greater than the moles of phenol employed inorder to introduce methylol groups in the intermediate stage. There isno indication that such groups appear in the final resin if prepared bythe use of an acid catalyst. It is possible that such groups may appearin the finished resins prepared solely with an alkaline catalyst; but wehave never been able to confirm this fact in an examination of a largenumber of resins prepared by ourselves. Our preference, however, is touse an acid-catalyzed resin, particularly employing aformadehyde-to-phenol ratio of 0.95 to 1.20 and, as far as we have beenable to determine, such resins are free from methylol groups. As amatter of fact, it is probable that in acid-catalyzed resinifications,the methylol structure may appear only momentarily at the very beginningof the reaction and in all probability is converted at once into a morecomplex structure during the intermediate stage.

One procedure which can be employed in the use of a new resin to prepareproducts for use in the process of the invention is to determine thehydroxyl value by the Verley-Bdlsing method or its equivalent. The resinas such, or in the form of a solution, as described, was then treatedwith a mixture of ethylene oxide and propylene oxide in presence of 0.5%to 2% of sodium methylate as a catalyst in step-wise fashion. The ratiosof propylene oxide and ethylene oxide employed correspond to the ratiosin the limiting points on the triangular graph, to wit, points I, 2, 3,4, 5, 6 and advantageously I, 1, 8 and 9. Our preference is to use thepropylene oxide and then the ethylene oxide, although useful productsare obtained by using ethylene oxide and then :propylene oxide or bycarrying out the oxyalkylation with the use of the two oxides at thesame time. Attention is directed to the fact that in the subsequentexamples reference is made to the step-wise addition of the alkyleneoxide, such as ethylene oxide. It is understood, of course, there is noobjection to the continuous addition of alkylene oxide until the desiredstage of reaction is reached. In fact, there may be less of a hazardinvolved and it is often advantageous to add the alkylene oxide, ormixture, slowly in a continuous stream and in such amount as to avoidexceeding the higher pressures noted in the various examples orelsewhere.

It may be well to emphasize the fact that when resins are produced fromdifunctional phenols and some of the higher aliphatic aldehydes, such asacetaldehyde, the resultant is a comparatively soft or pitch-like resinat Ordinary temperatures. Such resins become comparatively fluid at 110to 165 C., as a rule, and thus can be readily oxyalkylated, without theuse of a solvent.

Ordinarily, the oxyalkylation is carried out in autoclaves provided withagitators or stirring devices. We have found that the speed of theagitation markedly influences the time reaction. In some cases, thechange from slow speed agitation, for example, in a laboratoryautoclave, with a stirrer operating at a speed of 60 to 200 R. P. M., tohigh speed agitation with the stirrer operating at 250 to 350 R. P. M.,reduces the time required for oxyalkylation by one-half to two-thirds.Frequently xylene-soluble products which give insoluble products byprocedures employing comparatively slow speed agitation, give suitablehydrophile products. when produced by similar procedure, but with highspeed agitation, as a result, we believe, of the reduction in the timerequired, with consequent elimination or curtailment of opportunity forcuring or etherization. Even if the formation of an insoluble product isnot involved, it is frequently advantageous to speed up the reaction,thereby reducing production time, by increasing agitating speed. Inlarge scale operations, we have demonstrated that economicalmanufacturing results from continuous oxyalkylation, i. e., an operationin which the alkylene oxide is continuously fed to the reaction vessel,with high speed agitation, i. e., an agitator operating at 250 to 350 R.P. M. Continuous oxyalkylation, other conditions being the same, is morerapid than batch oxyalkylation, but the latter is ordinarily moreconvenient for laboratory operation.

In the continuous addition of ethylene oxide we have employed either acylinder of ethylene oxide without added nitrogen, provided that thepressure of the ethylene oxide was sufficiently great to pass into theautoclave, or we have used an arrangement, which, in essence, was theequivalent of an ethylene oxide cylinder with a means for injectingnitrogen so as to force the ethylene oxide in the manner of an ordinaryselzer bottle, combined with the means for either weighing the cylinderor measuring the ethylene oxide used volumetrically. In the case ofpropylene oxide we invariably used nitrogen pressure to cause the oxideto move into the autoclave.

Such procedure and arrangement for injecting liquids is, of course,conventional. In adding ethylene oxide or propylene oxide continuously,there is one precaution which must be taken at all times. The additionof the oxide must stop immediately if there is any indication thatreaction is stopped, or, obviously, if reaction is not started at thebeginning of the reaction period. Since the addition of ethylene oxideis invariably an exothermic reaction, whether or not reaction has takenplace, can be judged in the usual maner by observing (a) temperaturerise or drop, if any; and (b) amount of cooling water or other meansrequired to dissipate heat of reaction; thus, if there is a temperaturedropwithout the use of cooling water or equivalent, or if there is norise in temperature without using cooling water control, carefulinvestigation should be made.

The resins employed are prepared in the manner described in variousexamples, Nos. 1a

chart or graph of the attached figure.

through 103a, of our said Patent 2,499,370. In-

stead of being prepared on a laboratory scale, they were prepared in 10to 15-gallon electrovapor-heated synthetic resin pilot plant reactors,as manufactured by the Blaw-Knox Company, Pittsburgh, Pennsylvania, andcompletely described in their Bulletin No. 2087, issued in 1947, withspecified reference to Specification No. 71-3965.

In preparing the derivatives we have used the following procedurethroughout. Prepare the resins with a certain amount of solvent, such asxylene, present purely as a convenience. We have treated the resins withpropylene oxide and ethylene oxide in three different ways:

(a) Add the ethylene oxide first and then the propylene oxide;

(b) Add the propylene oxide first and then the ethylene oxide; and

(0) Use a mixture of propylene oxide and ethylene oxide, and make asingle addition.

In each case we have used an alkaline cata- :lyst equivalent toapproximately one-half percent to 1% of the total reaction mass in thefinal stage, or equivalent to one-fourth percent of alkaline catalystbased on final compound.

A number of resins were employed from a series of those resins whichcould be manufactured from commercially available phenols and aldehydes,such as Examples 1a, 2a, 3a, 4a, 5a,

24a, 25a, of Patent 2,499,370 and similar resins obtained from octylphenol, nonyl phenol, etc.

The commercially available aldehydes used were .usual manner.

Our exploration of products containing various proportions of the threeconstituents revealed that most effective compositions from thestandpoint of demulsification and, we believe, for other purposes,werefound within three relatively restricted areas, of which one is thearea I, 2, 3, 4, 5, 6, the products represented by which are the subjectmatter of this invention while the products represented by the other twoare the subject matter of other applications filed concurrentlyherewith.

We prepared a series of five different phenolformaldehyde resins, usingtertiary amyl phenol,

tertiary butyl phenol, tertiary octyl phenol, tertiary nonyl phenol andmenthyl phenol, and oxalkylated them in the proportions of one pound ofresin to fifteen pounds of ethylene oxide to .nine pounds of propyleneoxide, using twentyfive pounds of xylene as a solvent and two ounces offlake caustic soda as catalyst. The

.oxyalkylation of each of the resins was carried out in three differentWays:

((1) Adding all the ethylene oxide first and .then the propylene oxide;

(1)) Adding the propylene oxide first and then the ethylene oxide;

(0) Mixing the two oxides and adding them simultaneously.

We have prepared also a number of similar derivatives in which anotheraldehyde, such as acetaldehyde, propionic aldehyde, or furiural, replaceformaldehyde. What is said in regard to derivatives prepared fromformaldehyde is also true in regard to derivatives prepared from thesame, or various phenols and these other aldehydes. The subsequentoxyalkylation step, or steps, were the same. What has been said inregard to the effectiveness of derivatives derived from resins in whichformaldehyde enters into the manufacture, is true also in regard toresins in which these other aldehydes are used.

We again desire to point out that the amount of alkaline catalyst usedis not critical. This is true whether the catalyst be caustic soda,caustic potash, sodium methylate, or any other suitable catalyst. Theamount which we regularly employed has varied from 1%, based on theresin alone, to 1% based on the resin and oxides, although in manycases, the reaction has been speeded up by using approximately twicethis amount of caustic. We are inclined to believe that whenever theamount of caustic represents more than 2% of the reactants present,ignoring inert solvent, that there may be some tendency to form cyclicpolymer with the alkylene oxide, although this is purely a matter ofspeculation. For this reason, whether justified or not, We have usuallyavoided use of excess amounts of catalyst.

As we have stated, products of unusual value are produced when theircompositions are such that the three components are in proportionsrepresented by the ear I, 2, 3, 4, 5, 6, and advantageously l, I, 8, 9on the appended drawing. We have prepared a number of derivatives whichcome within this area and such derivatives are most effectivedemulsifiers, and effective for other purposes. It is understood, ofcourse, in each instance the composition is based on the assumption thatthe percentage by weight basis is on a statistical basis, which itobvious must be, and assumes completeness of reaction.

Having thus described our invention, what we claim as new and desire tosecure by Letters Patent is:

1. Hydrophile synthetic products, said hydrophile synthetic productsbeing oxyalkylation products of (a) both ethylene oxide and propyleneoxide; and (b) an oxyalkylation-susceptible, fusible, organicsolvent-soluble, water-insoluble phenol-aldehyde resin; said resin beingderived by reaction between a difunctional monohydric phenol and analdehyde having not over 8 carbon atoms and having one functional groupreactive toward said phenol; said resin being formed in the substantialabsence of trifunctional phenols; said phenol being of the formula inwhich R is a hydrocarbon radical having at least 4 and not more than 14carbon atoms and substituted in one of the positions ortho and para;said oxyalkylated resin being characterized by the introduction into theresin molecule of a plurality of divalent 021- and C3H6O radicals, withthe proviso that the composition of said hydrophile synthetic products,based on a statistical average and assuming completeness of reaction,and calculated back to the three oxyalkylation step reactants, i. e.,resin, ethylene oxide and propylene oxide, on a percentage weight basismust fall approximately within the area defined by the points I, 2, 3,4, 5, 6 of the chart in the accompanying drawing.

2. Hydrophile synthetic products, said hydrophile synthetic productsbeing oxyalkylation products of (a) both ethylene oxide and propyleneoxide; and (b) an oxyalkylation-susceptible, fusible, organicsolvent-soluble, water-insoluble phenol-aldehyde resin; said resin beingderived by reaction between a difunctional monohydric phenol and analdehyde having not over 8 carbon atoms and having one functional groupreactive toward said phenol; said resin being formed in the substantialabsence of trifunctional phenols; said phenol being of the formula inwhich R is a hydrocarbon radical having at least 4 and not more than 14carbon atoms and substituted in one of the positions ortho and para;said oxyalkylated resin being characterized by the introduction into theresin molecule of a plurality of divalent C2H4O and CsHeO radicals, withthe proviso that the composition of said hydrophile synthetic products,based on a statistical average and assuming completeness of reaction,and calculated back to the three oxyalkylation step reactants, i. e.,resin, ethylene oxide and propylene oxide, on a percentage weight basismust fall approximately within the area defined by the points I, I, 8, 9of the chart in the accompanying drawing.

3. The product of claim 1 wherein the aldehyde is formaldehyde.

4. The product of claim 1 wherein the aldehyde is formaldehyde and R isa butyl radical.

5. The product of claim 1 wherein the aldehyde is formaldehyde and R isan amyl radical.

6. The product of claim 1 wherein the aldehyde is formaldehyde and R isa nonyl radical.

MELVIN DE GROOTE. BERNHARD KEISER.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 2,076,624 De Groote Apr. 13, 19372,454,541 Bock Nov. 23, 1948 2,501,015 Wirtel Mar. 21, 1950

1. HYDROPHILE SYNTHETIC, PRODUCTS, SAID HYDROPHILE SYNTHETIC PRODUCTSBEING OXYALKYLATION PRODUCTS OF (A) BOTH ETHYLENE OXIDE AND PROPYLENEOXIDE; AND (B) AN OXYALKYLATION-SUSCEPTIBLE, FUSIBLE, ORGANICSOLVENT-SOLUBLE, WATER-SOLUBLE PHENOL-ALDEHYDE RESIN; SAID RESIN BEINGDERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND ANALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND HAVING ONE FUNCTIONAL GROUPREACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIALABSENCE OF TRIFUNCTIONAL PHENOLS; SAID PHENOL BEING OF THE FORMULA